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leaching kinetics of fluorine during the aluminum removal from spent Li-ion battery cathode materials

Journal of Environmental Sciences 2024年第4期138卷 312-325页

作者： Shengjie Li Jianxin Zhu Research Center for Eco-Environmental Sciences Chinese Academy of SciencesBeijing 100085China University of Chinese Academy of Sciences Beijing 100049China

The high content of aluminum(Al)impurity in the recycled cathode powder seriously affects the extraction efficiency of Nickel,Cobalt,Manganese,and Lithium resources and the actual commercial value of recycled materials,so Al removal is crucially important to conform to the industrial standard of spent Li-ion battery cathode materials.In this work,we systematically investigated the leaching process and optimum conditions associated with Al removal from the cathode powder materials collected in a wet cathode-powder peeling and recycling production line of spent Li-ion batteries(LIBs).Moreover,we specifically studied the leaching of fluorine(F)synergistically happened along with the removal process of Al,which was not concerned about in other studies,but one of the key factors affecting pollution prevention in the recovery process.The mechanism of the whole process including the leaching of Al and F from the cathode powder was indicated by using NMR,FTIR,and XPS,and a defluoridation process was preliminarily investigated in this study.The leaching kinetics of Al could be successfully described by the shrinking core model,controlled by the diffusion process and the activation energy was 11.14 kJ/mol.While,the leaching of F was attributed to the dissolution of LiPF6and decomposition of PVDF,and the kinetics associated was described by Avrami model.The interaction of Al and F is advantageous to realize the defluoridation to some degree.It is expected that our investigation will provide theoretical support for the large-scale recycling of spent LIBs.

关键词： Al removal F leaching Cathode powder Heating alkali leaching leaching kinetics

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Process and kinetics of the selective extraction of cobalt from high-silicon low-grade cobalt ores using ammonia leaching

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International Journal of Minerals,Metallurgy and Materials 2022年第2期29卷 218-227页

作者： Lei Tian Ao Gong Xuangao Wu Xiaoqiang Yu Zhifeng Xu Lijie Chen Institute of Green Metallurgy and Process Intensification Jiangxi University of Science and TechnologyGanzhou 341000China

An ammonia-based system was used to selectively leach cobalt(Co)from an African high-silicon low-grade Co ore,and the other elemental impurities were inhibited from leaching in this process.This process was simple and environmentally friendly.The results revealed that the leaching ratio of Co can reach up to 95.61%using(NH_(4))_(2)SO_(4)as a leaching agent under the following materials and conditions:(NH_(4))_(2)SO_(4)concentration 300 g/L,reductant dosage 0.7 g,leaching temperature 353 K,reaction time 4 h,and liquid-solid ratio 6 mL/g.The leaching kinetics of Co showed that the apparent activation energy of Co leaching was 76.07 kJ/mol(i.e.,in the range of 40-300 kJ/mol).This indicated that the leaching of Co from the Co ore was controlled by an interfacial chemical reaction,and then the developed leaching kinetics model of the Co can be expressed as 1-(1-α)^(1/3)=28.01×10~3×r_0^(-1)×C_((NH_(4))_(2)SO_(4))^(1.5)×exp(-76073/8.314 T)×t,whereαis the leaching ratio(%)of Co,r_0 is the average radius(m)of the Co ore particles,T is the temperature(K),and C_((NH_(4))_(2)SO_(4))is the initial reactant concentration(kg/m^(3)).

关键词： ammonia leaching leaching kinetics selective extraction cobalt

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kinetics of Magnesium Slag leaching by NH_(4)Cl

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Journal of Wuhan University of Technology(Materials Science) 2022年第5期37卷 787-793页

作者：毛帅东刘燕 ZHANG Ting'an School of Metallurgy Northeastern UniversityShenyang110819China Key Laboratory of Ecological Metallurgy of Multi—metal Intergrown Ores of Ministry of Education Shenyang110819China

The leaching kinetics of magnesium slag in ammonium chloride solutions was investigated.The effects of initial ammonium chloride concentration,liquid-solid ratio and reaction temperature on the leaching rate of calcium were determined.The results showed that the leaching rate increased with the increase in initial ammonium chloride concentration,reaction temperature and liquid-solid ratio.It was determined that the leaching rate fit the Avrami equation,and the leaching process was controlled by diffusion.The activation energy was 13.22 kJ/mol.

关键词： magnesium slag leaching kinetics ammonium chloride extracting

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Sulfuric acid leaching kinetics of South African chromite

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International Journal of Minerals,Metallurgy and Materials 2015年第3期22卷 233-240页

作者： Qing Zhao Cheng-jun Liu Pei-yang Shi Bo Zhang Mao-fa Jiang Qing-song Zhang Ron Zevenhoven Henrik Saxén Key Laboratory for Ecological Metallurgy of Multimetallic Ores (Ministry of Education) Northeastern University Thermal and Flow Engineering Laboratory bo Akademi University

The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching con- ditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional re- lationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. kinetics analysis revealed that the leach- ing process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ.mol-1.

关键词： chromite ore treatment sulfuric acid leaching kinetics physical models

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Effects of mechanical activation on the kinetics of terbium leaching from waste phosphors using hydrochloric acid

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Journal of Rare Earths 2017年第4期35卷 398-405页

作者：谭全银邓超李金惠 State Key Joint Laboratory of Environment Simulation and Pollution Control School of EnvironmentTsinghua University Beijing 100084China Basel Convention Regional Centre for Training and Technology Transfer for Asia and the Pacific Beijing 100084China

The effect of mechanical activation （MA） on the kinetics of terbium （Tb） leaching from waste phosphors using hydrochloric acid was investigated. leaching kinetics, such as apparent reaction rate, activation energy and reaction order, were determined using the shrinking-core model and the Arrhenius equation. Results obtained from experiments with different concentrations of HC1 and under different leaching temperatures were used for the determinations. The impacts of factors such as rotational speed, HC1 concen- tration and leaching temperature on the leaching rate of Tb were also discussed. The results showed that MA could dramatically increase the leaching rate of Tb from waste phosphors, and the apparent reaction rate （kap） of leaching was accelerated as well. For inactivated waste phosphors, the apparent activation energy （Eap） was 52.82±3.95 kJ/mol, indicating that the rate-controlling step of the leaching process was the chemical reaction. The Eap dropped to 25.96 ±3.90 kJ/mol and 10.96±2.79 k J/tool when the waste phosphors were mechanically activated at rotational speeds of 400 and 600 r/min, respectively; the leaching process transformed to a hybrid （chemical-reaction and diffusion） control process, and even a reagent-diffusion （through the product layer） control process. The apparent reaction order for Tb leaching from 400 r/min-activated waste phosphors was 2.49±0.11, and it decreased to 1. 16±0.17 when the rotational speed of 600 r/min was used. kinetics results indicated that MA could make Tb leaching occur spontaneously, and thc activation intensity of waste phosphors was strengthened with higher rotational speed.

关键词： terbium mechanical activation waste phosphors leaching kinetics hydrochloric acid rare earths

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Gold-leaching performance and mechanism of sodium dicyanamide

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International Journal of Minerals,Metallurgy and Materials 2021年第11期28卷 1759-1768页

作者： Gen-zhuang Li Jue Kou Yi Xing Yang Hu Wei Han Zi-yuan Liu Chun-bao Sun University of Science and Technology Beijing School of Civil and Resource EngineeringBeijing 100083China University of Science and Technology Beijing School of Energy and Environmental EngineeringBeijing 100083China

In this work,sodium dicyanamide(SD)was used as a leaching reagent for gold recovery,and the effects of the SD dosage and solution pH on the gold-leaching performance were investigated.A gold recovery of 34.8%was obtained when SD was used as the sole leaching reagent at a dosage of 15 kg/t.In the presence of a certain amount of potassium ferrocyanide(PF)in the SD solution,the gold recovery was found to increase from 34.8%to 57.08%.Using the quartz crystal microbalance with dissipation(QCM-D)technique,the leaching kinetics of SD with and without PF were studied.The QCM-D results indicate that the gold-leaching rate increased from 4.03 to 39.99 ng·cm^(–2)·min^(–1) when the SD concentration was increased from 0 to 0.17 mol/L,and increased from 39.99 to 272.62 ng·cm^(–2)·min^(–1) when 0.1 mol/L of PF was used in combination with SD.The pregnant solution in the leaching tests was characterized by X-ray photoelectron spectroscopy and electrospray mass spectrometry,which indicated that Au and(N(CN)2)–in the SD solution formed a series of metal complex ions,[AuNax(N(CN)2)x+2]–(x=1,2,3,or 4).

关键词： gold leaching sodium dicyanamide QCM-D leaching kinetics potassium ferrocyanide

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Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

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International Journal of Minerals,Metallurgy and Materials 2016年第5期23卷 491-500页

作者： Qing-quan Lin Guo-hua Gu Hui Wang Ren-feng Zhu You-cai Liu Jian-gang Fu School of Minerals Processing and Bioengineering Central South University School of Chemistry and Chemical Engineering Central South University

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfitric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leach- ing efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sul- furic acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respec- tively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent ac- tivation energy of 12.28 kJ·mol-l. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSOa4·H20.

关键词： manganese ore treamaent manganese carbonate leaching leaching kinetics manganese sulfate

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High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching

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Journal of Rare Earths 2021年第3期39卷 323-330,I0004页

作者： Qingsheng Liu Tao Tu Hao Guo Huajin Cheng Xuezhong Wang Faculty of Materials Metallurgy and Chemitry Jiangxi University of Science and TechnologyGanzhou 341000China Science School Jiangxi University of Science and TechnologyGanzhou 341000 China College of Materials Science and Engineering Jiangsu UniversityZhenjiang 212013China

Iron can not be recovered at high value because only rare earth elements are effectively recovered from NdFeB waste via oxidation roasting-hydrochloric acid leaching process.In this study,a new method for leaching NdFeB waste with oxalic acid was developed.The high-efficiency,simultaneous and high-value recovery of rare earth elements and iron was realized to simplify the process and improve the economic benefit.Results of the oxalic acid leaching experiments show that under the optimum leaching conditions at 90℃ for 6 h in the aqueous solution of oxalic acid(2 mol/L) with a liquid-solid ratio of60 mL/g,the iron leaching efficiency and precipitation rate of rare earth oxalate reach 93.89% and 93.17%,respectively.Rare earth oxalate and Fe(C_(2)O_(4))3^(3-) were left in the residue and the leaching solution,respectively.The leaching mechanism was further analyzed by characterising the leach residues obtained through X-ray powder diffraction(XRD) and scanning electron microscopy-energy dispersive X-ray spectroscopy(SEM-EDS).Results of the leaching kinetics study indicate that the process of oxalic acid leaching follows the shrinking nucleus model,and the leaching kinetics model is controlled by the mixed factors of diffusion and chemical reaction.The leaching residue was calcined at 850℃ for 3 h and then decomposed into rare earth oxide,which can be directly used to prepare rare earth alloy via molten salt electrolysis.For the leaching solution,ferric oxalate solution was reduced using Fe powder to prepare the ferrous oxalate(FeC_(2)O_(4)-2H_(2)O).

关键词： NdFeB waste Oxalic acid Orthogonal experiment leaching kinetics Reduction precipitation Rare earths

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Synergetic strengthening mechanism of ultrasound combined with calcium fluoride towards vanadium extraction from low-grade vanadium-bearing shale

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International Journal of Mining Science and Technology 2021年第6期31卷 1095-1106页

作者： Bo Chen Shenxu Bao Yimin Zhang School of Resources and Environmental Engineering Wuhan University of TechnologyWuhan 430070China Hubei Key Laboratory of Mineral Resources Processing and Environment Wuhan 430070China State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control Wuhan University of Science and TechnologyWuhan 430081China Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources Wuhan University of Science and TechnologyWuhan 430081China

The effect and mechanism of ultrasound and CaF_(2) on vanadium leaching from vanadium-bearing shale were investigated systematically.In consideration of the enhancement for vanadium recovery,the combination of ultrasound and CaF_(2)(66.28%) exerts more evident effects than ultrasound(26.97%) and CaF_(2)(60.35%) alone,demonstrating the synergetic effect of ultrasound and CaF_(2).Kinetic analysis manifests that the product layer diffusion controls vanadium leaching in ultrasound system without CaF_(2),however product layer diffusion and interfacial reaction is the rate-controlling step for vanadium leaching in other three leaching systems.The combination of ultrasound and CaF_(2) notably decreases the activation energy(E_(a)) from 62.03 to 27.61 kJ/mol,nevertheless individual CaF_(2) only reduces the E_(a) to 50.70 kj/mol.X-ray diffraction and fourier transform infrared spectrometer analyses show that the decomposition degree of the vanadium-bearing mica structure is the most significant in ultrasound and CaF_(2) system,proving the highest release degree of vanadium.Specific surface area and pore distribution combined with scanning electron microscope analyses reveal that the action of ultrasound and CaF_(2) would provide higher specific surface area,more abundant pores structure and cracks for the particles,which further prompts the rapid diffusion of H^(+),F^(-)and HF,and achieves the conspicuous improvement of vanadium leaching recovery.

关键词： Vanadium-bearing shale Ultrasound CaF_(2)addition Synergetic effect leaching kinetics

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leaching of Silica from Vanadium-Bearing Steel Slag in Sodium Hydroxide Solution

Leaching of Silica from Vanadium-Bearing Steel Slag in Sodiu...

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2010年全国冶金物理化学学术会议

作者：肖清贵陈寅裴丽丽徐红彬张懿 National Engineering Laboratory for Hydrometallurgical Clear Production Technology Chinese Academy of Sciences

This work aims to remove silica from vanadium-bearing steel slag by a leaching process.The leaching kinetics was studied in sodium hydroxide solutions.The samples used in experiments were obtained from Chende Xinxin Vataniam Titanium Chemical Co..The effects of the particle size,the ratio of solid to liquid,the concentration of sodium hydroxide solution and the leaching temperature were investigated. The shrinking core model was established to express the leaching kinetics of SiO from vanadium-bearing steel slag.The leaching data showed that the reaction was under chemical kinetics control and the activation energy for the process was found to be 36.4 kJ·mol.

关键词： vanadium-bearing steel slag leaching kinetics silica

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